CN113161506A - Perovskite light-emitting diode and preparation method thereof - Google Patents
Perovskite light-emitting diode and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000002105 nanoparticle Substances 0.000 claims abstract description 65
- 230000005525 hole transport Effects 0.000 claims abstract description 34
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- 239000010409 thin film Substances 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 105
- 238000004528 spin coating Methods 0.000 claims description 61
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- 239000000243 solution Substances 0.000 claims description 37
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 36
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 19
- 238000000137 annealing Methods 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 17
- 230000004048 modification Effects 0.000 claims description 16
- 239000012296 anti-solvent Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- HMSWAIKSFDFLKN-UHFFFAOYSA-N hexacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC HMSWAIKSFDFLKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- FIGVVZUWCLSUEI-UHFFFAOYSA-N tricosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCC FIGVVZUWCLSUEI-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 claims description 3
- WGTASENVNYJZBK-UHFFFAOYSA-N 3,4,5-trimethoxyamphetamine Chemical compound COC1=CC(CC(C)N)=CC(OC)=C1OC WGTASENVNYJZBK-UHFFFAOYSA-N 0.000 claims description 2
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 claims description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims 4
- 229910002367 SrTiO Inorganic materials 0.000 claims 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 2
- 239000011707 mineral Substances 0.000 claims 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 1
- 238000007738 vacuum evaporation Methods 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 13
- 238000005215 recombination Methods 0.000 abstract description 12
- 230000006798 recombination Effects 0.000 abstract description 12
- 230000007246 mechanism Effects 0.000 abstract description 7
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 31
- 239000007788 liquid Substances 0.000 description 9
- 238000006862 quantum yield reaction Methods 0.000 description 9
- 238000002189 fluorescence spectrum Methods 0.000 description 7
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000002739 cryptand Substances 0.000 description 6
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- 239000000463 material Substances 0.000 description 4
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- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910002370 SrTiO3 Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
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- 238000009792 diffusion process Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 150000002892 organic cations Chemical class 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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- H10K85/60—Organic compounds having low molecular weight
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- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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Abstract
The invention provides a perovskite light-emitting diode and a preparation method thereof, belonging to the technical field of light-emitting diodes. The perovskite light-emitting diode comprises the following components in sequence from bottom to top: a glass substrate having an ITO conductive film; a hole transport layer; a nanoparticle and/or crypt ether doped quasi-two-dimensional perovskite light emitting layer; an electron transport layer; a finishing layer; and an electrode. The invention also provides a preparation method of the perovskite light-emitting diode. The luminescent layer of the perovskite light-emitting diode is a quasi-two-dimensional perovskite thin film doped with nano particles and/or crypt ether, the structural order distribution in the quasi-two-dimensional perovskite thin film can be narrowed through doping, and the appearance of phases with lower or higher orders is reduced, so that the non-radiative recombination in the thin film is inhibited; based on this mechanism, a light emitting diode device having higher External Quantum Efficiency (EQE) is finally obtained.
Description
Technical Field
The invention belongs to the technical field of light emitting diodes, and particularly relates to a perovskite light emitting diode with a nano particle and/or crypt ether doped quasi-two-dimensional perovskite layer and a preparation method thereof.
Background
The traditional organic-inorganic hybrid three-dimensional perovskite material has the advantages of high carrier mobility, low trap state density and the like, and is widely applied to the photovoltaic field at present. However, since the exciton binding energy is low and it is difficult to limit the free diffusion of carriers, high radiative recombination efficiency cannot be obtained, making it impossible to directly apply to a light emitting diode. The construction of the quasi-two-dimensional perovskite is an effective way for improving the exciton binding energy of the perovskite material and enhancing the quantum confinement, thereby improving the radiative recombination efficiency. The multiple quantum well structure in the quasi-two-dimensional perovskite has stronger dielectric shielding and quantum confinement characteristics, and the exciton binding energy of the material can reach hundreds of meV, so the material has great application potential in the fields of light-emitting diodes, lasers and the like. However, the quasi-two-dimensional perovskite thin film prepared in general still has strong defect-induced non-radiative recombination inside, so that the thin film has a certain loss of fluorescence quantum yield and has excitation light intensity dependence. This is because the phenomenon that the order of the quasi-two-dimensional perovskite thin film prepared by the conventional solution method is impure inevitably occurs. Because of the solubility difference of different precursor components of the perovskite and the difference of the cation steric hindrance, the gradient distribution of quasi-two-dimensional orders in the direction vertical to the film is finally caused, wherein the perovskite phase of low order is mainly concentrated at the bottom of the film, and the high order phase is concentrated near the surface of the film. The wider quasi-two-dimensional order distribution can cause the fluorescence quantum yield of the film to be reduced, because the grain size of the perovskite phase with lower order in the film is relatively smaller, more grain boundaries are formed to cause the defect state density to be increased, and the non-radiative recombination is intensified; meanwhile, the perovskite phase with a higher order number in the film has lower exciton binding energy and quantum confinement capacity, excitons are easy to dissociate, the radiative recombination rate is reduced due to free diffusion of carriers, and the probability of defect-induced non-radiative recombination is increased. Therefore, regulating and controlling the structural order distribution in the quasi-two-dimensional perovskite thin film to narrow the order distribution so as to avoid the occurrence of a perovskite phase with a lower order or a higher order, and the method is an effective strategy for improving the fluorescence quantum yield of the thin film and the luminous efficiency of a device.
Disclosure of Invention
The luminescent layer of the perovskite light-emitting diode is a quasi-two-dimensional perovskite thin film doped with the nanoparticles and/or the crypt ether, the structural order distribution in the quasi-two-dimensional perovskite thin film can be narrowed through doping, the appearance of phases with lower or higher orders can be reduced, and the non-radiative recombination in the thin film can be inhibited; based on this mechanism, a light emitting diode device having higher External Quantum Efficiency (EQE) is finally obtained.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention provides a perovskite light emitting diode, which sequentially comprises the following components from bottom to top:
a glass substrate having an ITO (indium tin oxide) conductive thin film (ITO as a device anode);
a hole transport layer;
a perovskite light emitting layer;
an electron transport layer;
a finishing layer;
an electrode (as the device cathode);
it is characterized in that the preparation method is characterized in that,
the perovskite luminescent layer is a quasi-two-dimensional perovskite thin film doped with nanoparticles and/or crypt ether.
In the above technical solution, it is preferable that: the perovskite luminescent layer is PEA2FAn-1PbnBr3n+1Wherein PEA is phenylethylamine, FA is formamidine, n is the order of the quasi-two-dimensional perovskite structure, and the value of n is 3-8; the doped nano particles are ZrO with the grain diameter of 10-50 nm2、TiO2、ZnO、SnO2NiO or SrTiO3(ii) a The cryptate is 4,7,13,16,21, 24-hexaoxy-1, 10-diazabicyclo [8.8.8]]Hexacosane or 4,7,13,16, 21-pentaoxy-1, 10-diazabicyclo [8.8.5]]And twenty three alkanes.
In the above technical solution, it is preferable that: the hole transport layer is PVK (polyvinylcarbazole).
In the above technical solution, it is preferable that: the electron transport layer is TPBi (1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene).
In the above technical solution, it is preferable that: the modification layer is LiF.
In the above technical solution, it is preferable that: the electrode is Al.
In the above technical solution, it is preferable that: the thickness of the ITO conductive film is 80-150 nm, the thickness of the hole transport layer is 20-40 nm, the thickness of the perovskite luminescent layer is 30-150 nm, the thickness of the electron transport layer is 30-60 nm, the thickness of the modification layer is 0.8-1.6 nm, and the thickness of the electrode is 80-120 nm.
The invention also provides a preparation method of the perovskite light-emitting diode, which comprises the following steps:
(1) cleaning a substrate
Sequentially placing the glass substrate with the ITO conductive film in deionized water, acetone and isopropanol, respectively ultrasonically cleaning for 15-30 minutes, and then drying;
(2) preparation of PVK hole transport layer by spin coating method
Preparing a PVK chlorobenzene solution with the concentration of 5-15 mg/mL, and spin-coating the PVK chlorobenzene solution on the surface of the ITO conductive film obtained in the step (1), wherein the spin-coating speed is 2000-4500 rpm, and the spin-coating time is 30-50 seconds; then annealing for 20-40 minutes at 100-150 ℃, and finally cooling to room temperature; obtaining a PVK hole transport layer with the thickness of 20-40 nm;
(3) preparation of nano-particle and/or crypt ether doped perovskite luminescent layer by spin coating method
(3-1) firstly dispersing the nanoparticles in Dimethylformamide (DMF), preparing 0.2-1.0 mg/mL of DMF dispersion liquid of the nanoparticles, and ultrasonically dispersing for 4-8 hours; 0.1-0.6 mmol of PbBr20.08-0.48 mmol of FABr, 0.04-0.24 mmol of PEABr and 0.01-0.06 mmol of CH3NH3Dissolving Cl in a mixed solution of 0.5mL of the DMF dispersion solution of the nano particles and 0.5mL of dimethyl sulfoxide (DMSO); then spin-coating the solution on the surface of the PVK hole transport layer obtained in the step (2), wherein the spin-coating rotation speed is 4000-8000 rpm, the spin-coating time is 30-50 seconds, and 0.1-0.5 mL of ethyl acetate, diethyl ether, toluene or chlorobenzene is dripped on the rotating surface in the 10-15 seconds from the beginning of spin-coating to serve as an anti-solvent; finally, annealing for 10-30 minutes at 80-120 ℃ to obtain a perovskite luminescent layer with the thickness of 30-150 nm;
or (3-2) adding 0.1-0.6 mmol of PbBr20.08-0.48 mmol of FABr, 0.04-0.24 mmol of PEABr and 0.01-0.06 mmol of CH3NH3Cl was dissolved in a mixed solution of 0.5mL of DMF dispersion and 0.5mL of DMSO,adding 0.001-0.012 mmol of cryptand ether, and stirring at room temperature for 1-3 hours; then spin-coating the solution on the surface of the PVK hole transport layer obtained in the step (2), wherein the spin-coating rotation speed is 4000-8000 rpm, the spin-coating time is 30-50 seconds, and 0.1-0.5 mL of ethyl acetate, diethyl ether, toluene or chlorobenzene is dripped on the rotating surface in the 10-15 seconds from the beginning of spin-coating to serve as an anti-solvent; finally, annealing for 10-30 minutes at 80-120 ℃ to obtain a perovskite luminescent layer with the thickness of 30-150 nm;
or (3-3) firstly dispersing the nanoparticles in Dimethylformamide (DMF), preparing 0.2-1.0 mg/mL of DMF dispersion liquid of the nanoparticles, and ultrasonically dispersing for 4-8 hours; 0.1-0.6 mmol of PbBr20.08-0.48 mmol of FABr, 0.04-0.24 mmol of PEABr and 0.01-0.06 mmol of CH3NH3Dissolving Cl into a mixed solution of 0.5mL of nano particle DMF dispersion liquid and 0.5mL of dimethyl sulfoxide, adding 0.001-0.012 mmol of cryptand, and stirring at room temperature for 1-3 hours; then spin-coating the solution on the surface of the PVK hole transport layer obtained in the step (2), wherein the spin-coating rotation speed is 4000-8000 rpm, the spin-coating time is 30-50 seconds, and 0.1-0.5 mL of ethyl acetate, diethyl ether, toluene or chlorobenzene is dripped on the rotating surface in the 10-15 seconds from the beginning of spin-coating to serve as an anti-solvent; finally, annealing for 10-30 minutes at 80-120 ℃ to obtain a perovskite luminescent layer with the thickness of 30-150 nm;
(4) preparation of TPBi electron transport layer, LiF modification layer and Al electrode by vacuum evaporation method
At 1X 10-4~5×10-4And (3) sequentially evaporating a TPBi electron transport layer with the thickness of 30-60 nm, a LiF modification layer with the thickness of 0.8-1.6 nm and an Al electrode with the thickness of 80-120 nm on the surface of the perovskite luminescent layer obtained in the step (3) under the vacuum condition of Pa, so that the perovskite luminescent diode based on the doping of the nano particles and/or the cryptate is obtained.
In the technical scheme, the nano particles in the step (3) are ZrO with grain diameter of 10-50 nm2、TiO2、ZnO、SnO2NiO or SrTiO3。
In the technical scheme, the cryptate in the step (3) is 4,7,13,16,21, 24-hexaoxy-1, 10-diazabicyclo [8.8.8] hexacosane or 4,7,13,16, 21-pentaoxy-1, 10-diazabicyclo [8.8.5] tricosane.
The invention has the beneficial effects that:
the luminescent layer of the perovskite light-emitting diode is a quasi-two-dimensional perovskite thin film doped with nano particles and/or crypt ether, the structural order distribution in the quasi-two-dimensional perovskite thin film can be narrowed through doping, and the appearance of phases with lower or higher orders is reduced, so that the non-radiative recombination in the thin film is inhibited; based on this mechanism, a light emitting diode device having higher External Quantum Efficiency (EQE) is finally obtained.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a schematic structural view of a perovskite light emitting diode of the present invention.
FIG. 2 is a normalized fluorescence spectrum curve of the perovskite luminescent layer prepared in embodiments 1-4 of the present invention.
FIG. 3 is a graph comparing the fluorescence quantum yields of perovskite light-emitting layers prepared in examples 1 to 4 of the present invention.
FIG. 4 is an EQE-current density curve of perovskite light emitting diodes prepared in embodiments 1-4 of the present invention.
The reference numerals in fig. 1 are denoted as:
the solar cell comprises a 1-glass substrate, a 2-ITO conductive film, a 3-hole transport layer, a 4-perovskite luminescent layer, a 5-electron transport layer, a 6-modification layer and a 7-electrode.
Detailed Description
The invention firstly provides a quasi-two-dimensional perovskite light-emitting diode based on nano-particle and/or crypt ether doping, which sequentially comprises the following components from bottom to top: a glass substrate 1 having an ITO (indium tin oxide) conductive film 2 (ITO as a device anode); a hole transport layer 3; a nanoparticle and/or crypt ether doped quasi-two-dimensional perovskite light emitting layer 4; an electron transport layer 5; a finishing layer 6; electrode 7 (as the device cathode). The schematic structure of the device is shown in fig. 1.
The luminescent layer of the perovskite light-emitting diode device is a quasi-two-dimensional perovskite thin film doped with nano particles and/or crypt ether, the structural order distribution in the quasi-two-dimensional perovskite thin film can be narrowed through doping, the appearance of phases with lower or higher orders is reduced, and accordingly non-radiative recombination in the thin film is inhibited. Based on this mechanism, a light emitting diode device having higher External Quantum Efficiency (EQE) is finally obtained.
More specifically, the perovskite light emitting diode of the invention is sequentially composed of a glass substrate 1(ITO is used as a device anode) with an ITO (indium tin oxide) conductive film 2, a PVK (polyvinylcarbazole) hole transport layer 3, a nano particle and/or hole ether doped quasi-two-dimensional perovskite light emitting layer 4, a TPBi (1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene) electron transport layer 5, a LiF modification layer 6 and an Al electrode 7 (used as a device cathode) from bottom to top; the thickness of the ITO conductive film 2 is 80-150 nm, the thickness of the PVK hole transport layer 3 is 20-40 nm, the thickness of the nano particle and/or hole ether doped quasi-two-dimensional perovskite light emitting layer 4 is 30-150 nm, the thickness of the TPBi electron transport layer 5 is 30-60 nm, the thickness of the LiF modification layer 6 is 0.8-1.6 nm, and the thickness of the Al electrode 7 is 80-120 nm; the schematic structure of the device is shown in fig. 1.
In the device structure, the quasi-two-dimensional perovskite light-emitting layer 4 doped with the nano-particles and/or the crypt ether is PEA2FAn- 1PbnBr3n+1Wherein PEA: phenethylamine, FA: formamidine, n: the order of the quasi-two-dimensional perovskite structure is 3-8; the doped nano particles are ZrO with the grain diameter of 10-50 nm2、TiO2、ZnO、SnO2NiO or SrTiO3(ii) a The cryptate is 4,7,13,16,21, 24-hexaoxy-1, 10-diazabicyclo [8.8.8]]Hexacosane or 4,7,13,16, 21-pentaoxy-1, 10-diazabicyclo [8.8.5]]And twenty three alkanes.
The perovskite light emitting diode device of the invention based on the quasi two-dimensional perovskite light emitting layer 4 doped by nano particles and/or hole ether can obtain narrower quasi two-dimensional structure order distribution, and the main mechanism is as follows: the nano particles can improve the permeability of a perovskite layer, and promote the extraction of an anti-solvent to the solvent in the spin-coating film-anti-solvent cleaning process so as to inhibit the segregation of organic cations; the cryptate can selectively complex lead ions to slow down the crystallization speed, so that the integral crystallization of the film is more uniform. By utilizing the synergistic action mechanism of the two, narrower order distribution in the quasi-two-dimensional perovskite thin film can be further obtained, and the occurrence of perovskite phases with lower or higher orders is avoided.
The perovskite light-emitting diode of the invention has the main working principle that: under the external bias, electrons and holes are respectively injected from the cathode and the anode of the device and respectively flow through the electron transport layer 5 and the hole transport layer 3, and finally recombination and light emission are carried out on the perovskite light emitting layer 4. The quasi-two-dimensional perovskite light-emitting layer 4 based on nano-particles and/or crypt ether doping has a narrower structural order distribution, so that non-radiative recombination is effectively inhibited, and the device can obtain higher EQE.
The invention also provides a preparation method of the perovskite light-emitting diode, which comprises the following steps:
(1) cleaning a substrate
Sequentially placing the glass substrate 1 with the ITO conductive film 2 in deionized water, acetone and isopropanol, respectively ultrasonically cleaning for 15-30 minutes, and then drying;
(2) preparation of PVK hole transport layer 3 by spin coating
Preparing a PVK chlorobenzene solution with the concentration of 5-15 mg/mL, and spin-coating the PVK chlorobenzene solution on the surface of the ITO conductive film 2 obtained in the step (1), wherein the spin-coating speed is 2000-4500 rpm, and the spin-coating time is 30-50 seconds; then annealing for 20-40 minutes at 100-150 ℃, and finally cooling to room temperature; obtaining a PVK hole transport layer 3 with the thickness of 20-40 nm;
(3) preparation of nano-particle and/or crypt ether doped perovskite luminescent layer 4 by spin coating method
(3-1) firstly dispersing the nanoparticles in Dimethylformamide (DMF), preparing 0.2-1.0 mg/mL of DMF dispersion liquid of the nanoparticles, and ultrasonically dispersing for 4-8 hours; 0.1-0.6 mmol of PbBr20.08-0.48 mmol of FABr, 0.04-0.24 mmol of PEABr and 0.01-0.06 mmol of CH3NH3Dissolving Cl in a mixed solution of 0.5mL of the DMF dispersion solution of the nano particles and 0.5mL of dimethyl sulfoxide (DMSO); then spin-coating the solution on the surface of the PVK hole transport layer 3 obtained in the step (2), wherein the spin-coating speed is 4000-8000 rpm, and the spin-coating time is 30-EDripping 0.1-0.5 mL of ethyl acetate, ether, toluene or chlorobenzene serving as an anti-solvent on the rotating surface at the 10 th-15 th second from the beginning of spin coating for 50 seconds; finally, annealing for 10-30 minutes at 80-120 ℃ to obtain a perovskite luminescent layer 4 with the thickness of 30-150 nm;
or (3-2) adding 0.1-0.6 mmol of PbBr20.08-0.48 mmol of FABr, 0.04-0.24 mmol of PEABr and 0.01-0.06 mmol of CH3NH3Dissolving Cl in a mixed solution of 0.5mL of DMF dispersion liquid and 0.5mL of DMSO, adding 0.001-0.012 mmol of cryptand, and stirring at room temperature for 1-3 hours; then spin-coating the solution on the surface of the PVK hole transport layer 3 obtained in the step (2), wherein the spin-coating speed is 4000-8000 rpm, the spin-coating time is 30-50 seconds, and 0.1-0.5 mL of ethyl acetate, ether, toluene or chlorobenzene is dripped on the rotating surface in the 10-15 seconds from the beginning of spin-coating to serve as an anti-solvent; finally, annealing for 10-30 minutes at 80-120 ℃ to obtain a perovskite luminescent layer 4 with the thickness of 30-150 nm;
or (3-3) firstly dispersing the nanoparticles in Dimethylformamide (DMF), preparing 0.2-1.0 mg/mL of DMF dispersion liquid of the nanoparticles, and ultrasonically dispersing for 4-8 hours; 0.1-0.6 mmol of PbBr20.08-0.48 mmol of FABr, 0.04-0.24 mmol of PEABr and 0.01-0.06 mmol of CH3NH3Dissolving Cl into a mixed solution of 0.5mL of nano particle DMF dispersion liquid and 0.5mL of dimethyl sulfoxide, adding 0.001-0.012 mmol of cryptand, and stirring at room temperature for 1-3 hours; then spin-coating the solution on the surface of the PVK hole transport layer 3 obtained in the step (2), wherein the spin-coating speed is 4000-8000 rpm, the spin-coating time is 30-50 seconds, and 0.1-0.5 mL of ethyl acetate, ether, toluene or chlorobenzene is dripped on the rotating surface in the 10-15 seconds from the beginning of spin-coating to serve as an anti-solvent; finally, annealing for 10-30 minutes at 80-120 ℃ to obtain a perovskite luminescent layer 4 with the thickness of 30-150 nm;
(4) TPBi electron transport layer 5, LiF modification layer 6 and Al electrode 7 prepared by vacuum evaporation method
At 1X 10-4~5×10-4Sequentially evaporating TPBi electron transport layers 5 with the thickness of 30-60 nm on the surfaces of the perovskite light emitting layers obtained in the step (3) under the vacuum condition of Pa, wherein the thickness of the TPBi electron transport layers is 08-1.6 nm of LiF modification layer 6 and 80-120 nm of Al electrode 7, thereby obtaining the perovskite light-emitting diode based on nano particles and/or crypt ether doping.
Example 1:
sequentially placing a glass substrate 1 with an ITO conductive film 2 (the thickness is 100nm) in deionized water, acetone and isopropanol, respectively carrying out ultrasonic cleaning for 20 minutes, and then drying;
preparing a PVK chlorobenzene solution with the concentration of 10mg/mL, and then spin-coating the solution on the surface of the ITO conductive film 2 at the spin-coating speed of 4000 revolutions per minute for 40 seconds; then annealing for 30 minutes at 120 ℃, and finally cooling to room temperature; the thickness of the obtained PVK hole transport layer 3 is 25 nm;
0.2mmol of PbBr20.16mmol of FABr, 0.08mmol of PEABr and 0.02mmol of CH3NH3Dissolving Cl in a mixture of 0.5mL of DMF and 0.5mL of DMSO, and stirring at room temperature for 2 hours; then spin-coating the obtained solution on the surface of the PVK hole transport layer 3, wherein the spin-coating rotation speed is 7000 revolutions per minute, the spin-coating time is 40 seconds, and 0.15mL of ethyl acetate is dripped on the rotating surface at the 12 th second from the start of spin-coating to serve as an anti-solvent; finally annealing for 20 minutes at 80 ℃ to obtain a perovskite luminescent layer 4 with the thickness of 50 nm;
at 3X 10-4And (3) under the vacuum condition of Pa, sequentially evaporating a TPBi electron transport layer 5 with the thickness of 50nm, a LiF modification layer 6 with the thickness of 1nm and an Al electrode 7 with the thickness of 100nm on the surface of the perovskite luminous layer 4, and finishing the preparation of the device. The EQE-current density characteristic curve test was performed on the device, and the EQE peak value of the undoped device was 16.2%.
Example 2:
sequentially placing a glass substrate 1 with an ITO conductive film 2 (the thickness is 100nm) in deionized water, acetone and isopropanol, respectively carrying out ultrasonic cleaning for 20 minutes, and then drying;
preparing a PVK chlorobenzene solution with the concentration of 10mg/mL, and then spin-coating the solution on the surface of the ITO conductive film 2 at the spin-coating speed of 4000 revolutions per minute for 40 seconds; then annealing for 30 minutes at 120 ℃, and finally cooling to room temperature; the thickness of the obtained PVK hole transport layer 3 is 25 nm;
ZrO of grain diameter of 20nm2The nano particles are dispersed in DMF to prepare ZrO with 0.4mg/mL2Carrying out ultrasonic dispersion on the nano particle DMF dispersion liquid for 5 hours; 0.2mmol of PbBr20.16mmol of FABr, 0.08mmol of PEABr and 0.02mmol of CH3NH3Dissolving Cl in a mixture of 0.5mL of the DMF dispersion solution of the nanoparticles and 0.5mL of DMSO, and stirring at room temperature for 2 hours; then spin-coating the obtained solution on the surface of the PVK hole transport layer 3, wherein the spin-coating rotation speed is 7000 revolutions per minute, the spin-coating time is 40 seconds, and 0.15mL of ethyl acetate is dripped on the rotating surface at the 12 th second from the start of spin-coating to serve as an anti-solvent; finally annealing for 20 minutes at 80 ℃ to obtain a perovskite luminescent layer 4 with the thickness of 50 nm;
at 3X 10-4And (3) under the vacuum condition of Pa, sequentially evaporating a TPBi electron transport layer 5 with the thickness of 50nm, a LiF modification layer 6 with the thickness of 1nm and an Al electrode 7 with the thickness of 100nm on the surface of the perovskite luminous layer 4, and finishing the preparation of the device. The EQE-current density characteristic curve test is carried out on the device, the EQE peak value of the device doped with the nano particles in the perovskite layer reaches 18.4%, and compared with an undoped device, the EQE peak value is improved to a certain extent.
Example 3:
sequentially placing a glass substrate 1 with an ITO conductive film 2 (the thickness is 100nm) in deionized water, acetone and isopropanol, respectively carrying out ultrasonic cleaning for 20 minutes, and then drying;
preparing a PVK chlorobenzene solution with the concentration of 10mg/mL, and then spin-coating the solution on the surface of the ITO conductive film 2 at the spin-coating speed of 4000 revolutions per minute for 40 seconds; then annealing for 30 minutes at 120 ℃, and finally cooling to room temperature; the thickness of the obtained PVK hole transport layer 3 is 25 nm;
0.2mmol of PbBr20.16mmol of FABr, 0.08mmol of PEABr and 0.02mmol of CH3NH3Cl was dissolved in a mixture of 0.5mL DMF and 0.5mL DMSO and 0.003 mmol cryptand 4,7,13,16,21, 24-hexaoxy-1, 10-diazabicyclo [8.8.8] was added]The hexacosane is stirred for 2 hours at room temperature; the obtained solution was then spin-coated on the surface of the PVK hole transport layer 3 at 7000 rpm for 40 seconds in the direction of 12 seconds from the start of the spin-coating0.15mL of ethyl acetate is dripped on the surface of the substrate as an anti-solvent; finally annealing for 20 minutes at 80 ℃ to obtain a perovskite luminescent layer 4 with the thickness of 50 nm;
at 3X 10-4And (3) under the vacuum condition of Pa, sequentially evaporating a TPBi electron transport layer 5 with the thickness of 50nm, a LiF modification layer 6 with the thickness of 1nm and an Al electrode 7 with the thickness of 100nm on the surface of the perovskite luminous layer 4, and finishing the preparation of the device. The EQE-current density characteristic curve test is carried out on the device, the EQE peak value of the device with the perovskite layer doped with the cave ether reaches 19.3%, and the device is improved to a certain extent compared with an undoped device.
Example 4:
sequentially placing a glass substrate 1 with an ITO conductive film 2 (the thickness is 100nm) in deionized water, acetone and isopropanol, respectively carrying out ultrasonic cleaning for 20 minutes, and then drying;
preparing a PVK chlorobenzene solution with the concentration of 10mg/mL, and then spin-coating the solution on the surface of the ITO conductive film 2 at the spin-coating speed of 4000 revolutions per minute for 40 seconds; then annealing for 30 minutes at 120 ℃, and finally cooling to room temperature; the thickness of the obtained PVK hole transport layer 3 is 25 nm;
ZrO of grain diameter of 20nm2The nano particles are dispersed in DMF to prepare ZrO with 0.4mg/mL2Carrying out ultrasonic dispersion on the nano particle DMF dispersion liquid for 5 hours; 0.2mmol of PbBr20.16mmol of FABr, 0.08mmol of PEABr and 0.02mmol of CH3NH3Cl was dissolved in 0.5mL of the mixture of the nanoparticle DMF dispersion and 0.5mL of DMSO, and 0.003mmol of cryptand 4,7,13,16,21, 24-hexaoxy-1, 10-diazabicyclo [8.8.8]]The hexacosane is stirred for 2 hours at room temperature; then spin-coating the obtained solution on the surface of the PVK hole transport layer 3, wherein the spin-coating rotation speed is 7000 revolutions per minute, the spin-coating time is 40 seconds, and 0.15mL of ethyl acetate is dripped on the rotating surface at the 12 th second from the start of spin-coating to serve as an anti-solvent; finally annealing for 20 minutes at 80 ℃ to obtain a perovskite luminescent layer 4 with the thickness of 50 nm;
at 3X 10-4And (3) under the vacuum condition of Pa, sequentially evaporating a TPBi electron transport layer 5 with the thickness of 50nm, a LiF modification layer 6 with the thickness of 1nm and an Al electrode 7 with the thickness of 100nm on the surface of the perovskite luminous layer 4, and finishing the preparation of the device. To the deviceAccording to an EQE-current density characteristic curve test, the EQE peak value of the device with the perovskite layer doped with the nano particles and the crypt ether simultaneously reaches 21.2%, and compared with the device with the nano particles or the crypt ether doped independently, the EQE peak value is further improved.
FIG. 2 is a normalized fluorescence spectrum curve of the perovskite luminescent layer prepared in embodiments 1-4 of the present invention, wherein: curve 1 represents the normalized fluorescence spectrum of the perovskite luminescent layer prepared in example 1, the perovskite layer being undoped with nanoparticles or cryptates; curve 2 represents the normalized fluorescence spectrum of the perovskite luminescent layer prepared in example 2, the perovskite layer being doped with nanoparticles and not with cryptates; curve 3 represents the normalized fluorescence spectrum of the perovskite luminescent layer prepared in example 3, the perovskite layer being undoped with nanoparticles and doped with cryptate; curve 4 represents the normalized fluorescence spectrum of the perovskite luminescent layer prepared in example 4, the perovskite layer being doped with both nanoparticles and cryptates;
as shown in the figure, compared with the perovskite layer which is not doped, the single doping of the nano particles or the cryptate can generate blue shift of the luminous peak of the film, and the half-peak width is reduced, namely the phenomenon that the order distribution in the quasi-two-dimensional perovskite film is narrowed; when the nano particles and the cryptate ether are doped at the same time, the peak value of the fluorescence spectrum continues to carry out blue shift, which shows that the action mechanisms of the nano particles and the cryptate ether can be mutually superposed, and the order distribution is further narrowed;
FIG. 3 is a comparison of fluorescence quantum yields of perovskite luminescent layers prepared in examples 1 to 4 of the present invention;
as shown, the fluorescence quantum yield of undoped perovskite layer in example 1 was 77.2%; the nano-particles are doped in the example 2, and the fluorescence quantum yield of the perovskite layer of the undoped cryptate is 84.5 percent; the fluorescence quantum yield of the perovskite layer doped with the cryptate is 86.2 percent when the nano particles are not doped in the embodiment 3; the fluorescence quantum yield of the perovskite layer doped with the nanoparticles and the cryptate in example 4 is 90.2%;
fig. 4 is an EQE-current density curve of the perovskite light emitting diode prepared in embodiments 1 to 4 of the present invention, wherein: curve 1 represents the EQE-current density curve for the perovskite light emitting diode prepared in example 1; curve 2 represents the EQE-current density curve for the perovskite light emitting diode prepared in example 2; curve 3 represents the EQE-current density curve for the perovskite light emitting diode prepared in example 3; curve 4 represents the EQE-current density curve for the perovskite light emitting diode prepared in example 4;
as shown in the figure, in the device in which the perovskite layer is not doped, the EQE curve is the lowest, and the peak value is 16.3%; after the nano particles or the cryptate ether are respectively doped, the EQE is improved, and the peak values respectively reach 18.4 percent and 19.3 percent; after the nano particles and the cryptate ether are doped at the same time, the EQE can be continuously improved, and the peak value reaches 21.2%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
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